Functional Groups, a Short List 1 Oxygen-Containing Acetal/Ketal

Total Page:16

File Type:pdf, Size:1020Kb

Functional Groups, a Short List 1 Oxygen-Containing Acetal/Ketal Functional Groups, A Short List Oxygen-containing Diketene Acetal/ketal Acid anhydride Ester Acyl halide Ether X = Cl, Br, I Ethylenedioxy- (crown ether) Acylal Hemiacetal/Hemiketal Alcohol Homoallylic Carbonate Hydroperoxide Carboxylic acid/carboxylate anion Ketene Chloroformate ester Ketone/aldehyde Dicarbonate Lactone 1 Methylenedioxy- Amide Orthocarbonate ester Amidine Orthoester Amidrazone Peroxide Amine Ynol* *Highly unstable, tautomer of ketene Azide Ynone Azine Nitrogen-containing Azo group Acylurea Azoxy Aldimine (primary/secondary) Carbamate 2 Carbazide Hydroxamic acid Carbodiimide Imide Carboximidate Imidic acid Cyanate Isocyanate Cyanimide Isonitrile Diazo group Ketenimine Enamide Ketimine (primary/secondary) Enamine Lactam Hydrazone Nitrile (cyanide) Nitrite 3 Nitrosamine Dithiocarboxylic acid ester Nitroso Isothiocyanate Oxime S-nitrosothiol Sulfate Semicarbazide Sulfenamide Semicarbazone Sulfenyl chloride Triazene Sulfinic acid Sulfur-containing Sulfite Disulfide Sulfonate ester Dithiocarbamate Sulfone Dithiocarboxylic acid 4 Sulfonic acid Thioketene Sulfonyl Thiol X = Cl, Br, I Thiolester Sulfoxide Thionoester Sulfuryl Thiosemicarbazide X = Cl, Br, I Thial Thiourea Thiocarboxylic acid (O) Phosphorus-containing Thiocarboxylic acid (S) Phosphate Thiocyanate Phosphine Thioether (sulfide) Phosphodiester Thioketone 5 Phosphonate Siloxy group Silyl chloride Phosphonic acid Silyl ether Phosphonite Silyl hydride Phosphoramide Phosphoramidite Alkyl groups Adamantyl group Silicon-containing Silanol Allyl group Benzyl group (–Bn) Silene Butyl group Silole s-Butyl group 6 Isobutyl group Boron-containing Borinic acid t-Butyl group Borinic ester Crotyl group (cis/trans) Boronic acid Ethyl group Boronic ester Isoprene Propyl group Miscellaneous Acetoxy (–OAc) Isopropyl group Acetyl group (–Ac) Neopentyl group Phenyl group (–Ph) Acryloyl group Propargyl group Acyl group Vinyl group 7 Benzoyl group (–Bz) Telluroketone* Tellurol* Enediyne *Tellurium-containing functional groups are highly unstable Tosyl group (–Ts) Nonaflate group Tosylate (–OTs) Selenenic acid Seleninic acid Triflate group (–Tf) Selenol Vanillyl group Selenonic acid Selone Functional groups featuring tautomerism Tautomerization of some of the functional groups found in the notes Tellurocyanate* Keto-enol tautomerization Telluroester* 8 Imine-enamine tautomerization Azetidine Oxetane Amide-imidic acid tautomerization Lactam-lactim tautomerization Oxolane / Tetrahydrofuran Pyrrolidine / Azolidine Nitroso-oxime tautomerization Tetrahydrothiophene Ketene-ynol tautomerization Oxole / Furan Heterocycles Epoxide (oxirane) Azole / Pyrrole Aziridine Thiophene Episulfide / Thiirane Imidazole Dioxirane Pyrazole 9 Pyridine Isoxazole Pyrimidine Oxazole Pyridazine Thiazole Pyrazine Triazole (1,2,3 and 1,2,4) Pyran Tetrahydropyran 4H-Pyran Piperidine / azinane Tetrahydrothiopyran Morpholine Dioxane 10 .
Recommended publications
  • De Novo Biosynthesis of Terminal Alkyne-Labeled Natural Products
    De novo biosynthesis of terminal alkyne-labeled natural products Xuejun Zhu1,2, Joyce Liu2,3, Wenjun Zhang1,2,4* 1Department of Chemical and Biomolecular Engineering, 2Energy Biosciences Institute, 3Department of Bioengineering, University of California, Berkeley, CA 94720, USA. 4Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. *e-mail:[email protected] 1 Abstract: The terminal alkyne is a functionality widely used in organic synthesis, pharmaceutical science, material science, and bioorthogonal chemistry. This functionality is also found in acetylenic natural products, but the underlying biosynthetic pathways for its formation are not well understood. Here we report the characterization of the first carrier protein- dependent terminal alkyne biosynthetic machinery in microbes. We further demonstrate that this enzymatic machinery can be exploited for the in situ generation and incorporation of terminal alkynes into two natural product scaffolds in E. coli. These results highlight the prospect for tagging major classes of natural products, including polyketides and polyketide/non-ribosomal peptide hybrids, using biosynthetic pathway engineering. 2 Natural products are important small molecules widely used as drugs, pesticides, herbicides, and biological probes. Tagging natural products with a unique chemical handle enables the visualization, enrichment, quantification, and mode of action study of natural products through bioorthogonal chemistry1-4. One prevalent bioorthogonal reaction is
    [Show full text]
  • Phospholipid:Diacylglycerol Acyltransferase: an Enzyme That Catalyzes the Acyl-Coa-Independent Formation of Triacylglycerol in Yeast and Plants
    Phospholipid:diacylglycerol acyltransferase: An enzyme that catalyzes the acyl-CoA-independent formation of triacylglycerol in yeast and plants Anders Dahlqvist*†‡, Ulf Ståhl†§, Marit Lenman*, Antoni Banas*, Michael Lee*, Line Sandager¶, Hans Ronne§, and Sten Stymne¶ *Scandinavian Biotechnology Research (ScanBi) AB, Herman Ehles Va¨g 2 S-26831 Svaloˆv, Sweden; ¶Department of Plant Breeding Research, Swedish University of Agricultural Sciences, Herman Ehles va¨g 2–4, S-268 31 Svalo¨v, Sweden; and §Department of Plant Biology, Uppsala Genetic Center, Swedish University of Agricultural Sciences, Box 7080, S-750 07 Uppsala, Sweden Edited by Christopher R. Somerville, Carnegie Institution of Washington, Stanford, CA, and approved March 31, 2000 (received for review February 15, 2000) Triacylglycerol (TAG) is known to be synthesized in a reaction that acid) and epoxidated fatty acid (vernolic acid) in TAG in castor uses acyl-CoA as acyl donor and diacylglycerol (DAG) as acceptor, bean (Ricinus communis) and the hawk’s-beard Crepis palaestina, and which is catalyzed by the enzyme acyl-CoA:diacylglycerol respectively. Furthermore, a similar enzyme is shown to be acyltransferase. We have found that some plants and yeast also present in the yeast Saccharomyces cerevisiae, and the gene have an acyl-CoA-independent mechanism for TAG synthesis, encoding this enzyme, YNR008w, is identified. which uses phospholipids as acyl donors and DAG as acceptor. This reaction is catalyzed by an enzyme that we call phospholipid:dia- Materials and Methods cylglycerol acyltransferase, or PDAT. PDAT was characterized in Yeast Strains and Plasmids. The wild-type yeast strains used were microsomal preparations from three different oil seeds: sunflower, either FY1679 (MAT␣ his3-⌬200 leu2-⌬1 trp1-⌬6 ura3-52) (9) or castor bean, and Crepis palaestina.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 6,037,477 Ishii Et Al
    USOO6037477A United States Patent (19) 11 Patent Number: 6,037,477 Ishii et al. (45) Date of Patent: Mar. 14, 2000 54) OXIDATION PROCESS OF ETHERS 838909 2/1996 Japan. 75 Inventors: Yasutaka Ishii, 19-21, OTHER PUBLICATIONS Besshohonmachi, Takatsuki-shi, Osaka Ishii et al., J. Org. Chem., vol. 61, pp. 4520-4526 (1996). 569-1112, Tatsuya Nakano, Himeji, Yoshino et al., J. Org. Chem., vol. 62, No. 20, pp. both of Japan 6810–6813 (Oct. 1997). Takeno et al., Aerobic Oxidation by Using N-hydroxyph 73 Assignees: Daicel Chemical Industries, Ltd.; thalimide, 67th Spring Annual Meeting of Chemical Society Yasutaka Ishii, both of Osaka, Japan of Japan, Lecture Draft II, Dec. 1994. 21 Appl. No.: 09/074,604 Primary Examiner Johann Richter ASSistant Examiner-Dominic Keating 22 Filed: May 8, 1998 Attorney, Agent, or Firm-Birch, Stewart, Kolasch & Birch, 30 Foreign Application Priority Data LLP May 13, 1997 JP Japan .................................... 9-122526 57 ABSTRACT 51) Int. Cl." .................. C07D 207/404; CO7D 207/448; An ether is oxidized with oxygen under an oxidation catalyst CO7D 487/06; CO7D 207/444 comprising an imide compound (Such as 52 U.S. Cl. .......................... 548/545; 548/548; 548/549; N-hydroxyphthalimide) or the imide compound and a 548/453 co-catalyst to produce the corresponding chain or cyclic 58 Field of Search ..................................... 548/545, 548, ester or anhydride. The co-catalyst may be a transition metal 548/549 compound. The above proceSS provides a process for oxi dizing an ether by oxygen efficiently to produce the corre 56) References Cited sponding oxide (Such as an ester, an hydride) with high conversion and Selectivity.
    [Show full text]
  • The Oxidation of Secondary Alcohols by Dimethyldioxirane: Re-Examination of Kinetic Isotope Effects
    Heterocycl. Commun., Vol. 16(4-6), pp. 217–220, 2010 • Copyright © by Walter de Gruyter • Berlin • New York. DOI 10.1515/HC.2010.016 Preliminary Communication The oxidation of secondary alcohols by dimethyldioxirane: re-examination of kinetic isotope effects A lfons L. Baumstark *, P edro C. Vasquez, Mark 1991 ; Denmark and Wu , 1998 ; Frohn et al. , 1998 ) or in an Cunningham a and Pamela M. Leggett-Robinson b isolated solution (Murray and Jeyaraman , 1985 ; Baumstark and McCloskey , 1987 ). The epoxidation of alkenes and het- Department of Chemistry , Center for Biotech and Drug eroatom oxidation by isolated solutions of 1 in acetone have Design, Georgia State University, Atlanta, Georgia been extensively investigated (Murray and Jeyaraman , 1985 ; 30302-4098 , USA Baumstark and McCloskey , 1987 ; Baumstark and Vasquez , * Corresponding author 1988 ; Winkeljohn et al. , 2004 , 2007 ). Dioxiranes can also e-mail: [email protected] insert oxygen into unactivated CH bonds of alkanes (Murray et al. , 1986 ). However, this important reaction generally requires a dioxirane more reactive than dimethyldioxirane to Abstract be of utility (Kuck et al. , 1994 ; D ’ Accolti et al., 2003 ). The oxidation of secondary alcohols by dimethyldioxirane, 1 , to The kinetic isotope effects for the oxidation of a series of ketones can be achieved in high yield under mild conditions deuterated isopropanols and α -trideuteromethyl benzyl alco- and with convenient reaction times (Kovac and Baumstark , hol by dimethyldioxirane ( 1 ) to the corresponding ketones 1994 ; Cunningham et al. , 1998; Baumstark, 1999 ). Two were determined in dried acetone at 23 ° C. A primary kinetic mechanistic extremes have been proposed for secondary alco- isotope effect (PKIE) of 5.2 for the oxidation of isopropyl- hol oxidation by 1 : a) concerted insertion (Mello et al.
    [Show full text]
  • Organic Chemistry
    Wisebridge Learning Systems Organic Chemistry Reaction Mechanisms Pocket-Book WLS www.wisebridgelearning.com © 2006 J S Wetzel LEARNING STRATEGIES CONTENTS ● The key to building intuition is to develop the habit ALKANES of asking how each particular mechanism reflects Thermal Cracking - Pyrolysis . 1 general principles. Look for the concepts behind Combustion . 1 the chemistry to make organic chemistry more co- Free Radical Halogenation. 2 herent and rewarding. ALKENES Electrophilic Addition of HX to Alkenes . 3 ● Acid Catalyzed Hydration of Alkenes . 4 Exothermic reactions tend to follow pathways Electrophilic Addition of Halogens to Alkenes . 5 where like charges can separate or where un- Halohydrin Formation . 6 like charges can come together. When reading Free Radical Addition of HX to Alkenes . 7 organic chemistry mechanisms, keep the elec- Catalytic Hydrogenation of Alkenes. 8 tronegativities of the elements and their valence Oxidation of Alkenes to Vicinal Diols. 9 electron configurations always in your mind. Try Oxidative Cleavage of Alkenes . 10 to nterpret electron movement in terms of energy Ozonolysis of Alkenes . 10 Allylic Halogenation . 11 to make the reactions easier to understand and Oxymercuration-Demercuration . 13 remember. Hydroboration of Alkenes . 14 ALKYNES ● For MCAT preparation, pay special attention to Electrophilic Addition of HX to Alkynes . 15 Hydration of Alkynes. 15 reactions where the product hinges on regio- Free Radical Addition of HX to Alkynes . 16 and stereo-selectivity and reactions involving Electrophilic Halogenation of Alkynes. 16 resonant intermediates, which are special favor- Hydroboration of Alkynes . 17 ites of the test-writers. Catalytic Hydrogenation of Alkynes. 17 Reduction of Alkynes with Alkali Metal/Ammonia . 18 Formation and Use of Acetylide Anion Nucleophiles .
    [Show full text]
  • Novel Approach to Introduce Alkyl Chains Into PEDOT:PSS and Its Effect on the Performance As a Flexible Electrode
    applied sciences Article Novel Approach to Introduce Alkyl Chains into PEDOT:PSS and Its Effect on the Performance as a Flexible Electrode In-Seong Hwang 1, Chul-Woo Park 1, Hye-In Kang 1, Sung-yoon Joe 2, Na-Young Pak 3 and Dae-won Chung 1,* 1 Department of Polymer Engineering, College of Engineering, The University of Suwon, Hwaseong-si 18323, Korea; [email protected] (I.-S.H.); [email protected] (C.-W.P.); [email protected] (H.-I.K.) 2 Center of Advanced Materials Analysis, The University of Suwon, Hwaseong-si 18323, Korea; [email protected] 3 EverChemTech Co., Ltd., 38, Cheongwonsandan 7-gil, Mado-myeon, Hwaseong-si 18323, Korea; [email protected] * Correspondence: [email protected]; Tel.: +81-312-202-156 Abstract: We here report a synthetic route to introduce alky chains into poly (3,4-ethylenedioxythio- phene):poly (4-styrenesulfonate) (PEDOT:PSS) by the reaction with epoxyalkanes. The reaction was analyzed by FT-IR, TGA, and XPS studies, and the conductivities of derivatives were discussed as a function of the length of alkyl chains. PEDOT:PSS-C6, which is the product from a reaction with epoxyhexane, was well dispersed in methanol and transparent films from this dispersion were successfully prepared. PEDOT:PSS-C6 film showed an increase in hydrophobicity, resulting in enhanced water resistance compared to pristine PEDOT:PSS film, and a morphological study of the film exhibited clear phase separation similar to PEDOT:PSS doped by DMSO. We also observed an improvement in the conductivity and flexibility of PEDOT:PSS-C6 film compared to those of Citation: Hwang, I.-S.; Park, C.-W.; pristine PEDOT:PSS film.
    [Show full text]
  • Acetal (POM) Chemical Compatibility Chart From
    ver 31-Mar-2020 Acetal (POM) Chemical Compatibility Chart Chemical Chemical Acetaldehyde A Ammonium Acetate C Acetamide A Ammonium Bifluoride D Acetate Solvents A Ammonium Carbonate D Acetic Acid D Ammonium Caseinate D Acetic Acid, 20% C Ammonium Chloride, 10% B Acetic Acid, 80% D Ammonium Hydroxide D Acetic Acid, Glacial D Ammonium Nitrate, 10% A Acetic Anhydride D Ammonium Oxalate B Acetone A Ammonium Persulfate D Acetyl Chloride, dry D Ammonium Phosphate, Dibasic B Acetylene A Ammonium Phosphate, Monobasic B Alcohols: Amyl A Ammonium Phosphate, Tribasic B Alcohols: Benzyl A Ammonium Sulfate B Alcohols: Butyl A Ammonium Sulfite D Alcohols: Diacetone A Ammonium Thiosulfate B Alcohols: Ethyl A Amyl Acetate B Alcohols: Hexyl A Amyl Alcohol A Alcohols: Isobutyl A Amyl Chloride A Alcohols: Isopropyl A Aniline A Alcohols: Methyl A Aniline Oil D Alcohols: Octyl A Anise Oil D Alcohols: Propyl (1-Propanol) A Antifreeze D Aluminum chloride, 20% C Aqua Regia (80% HCl, 20% HNO3) D Aluminum Fluoride C Aromatic Hydrocarbons A Aluminum Hydroxide A Arsenic Acid D Aluminum Nitrate B Asphalt B Aluminum Potassium Sulfate, 10% C Barium Carbonate A Aluminum Potassium Sulfate, 100% C Barium Chloride A Aluminum Sulfate, 10% B Barium Cyanide B Alums C Barium Hydroxide D Amines D Barium Nitrate B Ammonia, 10% (Ammonium Hydroxide) C Barium Sulfate B Ammonia, 10% D Barium Sulfide A Ammonia, anhydrous D Bay Oil D Ammonia, liquid D Beer A Ammonia Nitrate C Beet Sugar Liquids B Key to General Chemical Resistance – All data is based on ambient or room temperature conditions, about 64°F (18°C) to 73°F (23°C) A = Excellent C = Fair - Moderate Effect, not recommended B= Good - Minor Effect, slight corrosion or discoloration D = Severe Effect, not recommended for ANY use It is the sole responsibility of the system designer and user to select products suitable for their specific application requirements and to ensure proper installation, operation, and maintenance of these products.
    [Show full text]
  • Chapter 13 Reactions of Arenes Electrophilic Aromatic Substitution
    CH. 13 Chapter 13 Reactions of Arenes Electrophilic Aromatic Substitution Electrophiles add to aromatic rings in a fashion somewhat similar to the addition of electrophiles to alkenes. Recall: R3 R4 E Y E Y C C + E Y R1 C C R4 R1 C C R4 − R2 R1 δ+ δ R2 R3 R2 R3 In aromatic rings, however, we see substitution of one of the benzene ring hydrogens for an electrophile. H E + E Y + Y H δ+ δ− The mechanism is the same regardless of the electrophile. It involves two steps: (1) Addition of the electrophile to form a high-energy carbocation. (2) Elimination of the proton to restore the aromatic ring system. H H H H slow E Y + Y step 1 + E δ+ δ− high energy arenium ion H H step 2 fast E E + Y + Y H The first step is the slow step since the aromaticity of the benzene ring system is destroyed on formation of the arenium ion intermediate. This is a high energy species but it is stabilized by resonance with the remaining two double bonds. The second step is very fast since it restores the aromatic stabilization. 1 CH. 13 H H H H H H E E E There are five electrophilic aromatic substitution reactions that we will study. (1) Nitration H NO2 H2SO4 + HNO3 (2) Sulfonation H SO3H + H2SO4 (3) Halogenation with bromine or chlorine H X FeX3 X = Br, Cl + X2 (4) Friedel-Crafts Alkylation H R AlX + RX 3 (5) Friedel-Crafts Acylation O H O C AlX3 R + Cl C R 2 CH.
    [Show full text]
  • INDOLES from 2-METHYLNITROBENZENES by CONDENSATION with FORMAMIDE ACETALS FOLLOWED by REDUCTION: 4-BENZYLOXYINDOLE [1H-Indole, 4-(Phenylmethoxy)-]
    DOI:10.15227/orgsyn.063.0214 Organic Syntheses, Coll. Vol. 7, p.34 (1990); Vol. 63, p.214 (1985). INDOLES FROM 2-METHYLNITROBENZENES BY CONDENSATION WITH FORMAMIDE ACETALS FOLLOWED BY REDUCTION: 4-BENZYLOXYINDOLE [1H-Indole, 4-(phenylmethoxy)-] Submitted by Andrew D. Batcho1 and Willy Leimgruber2. Checked by David J. Wustrow and Andrew S. Kende. 1. Procedure A. 6-Benzyloxy-2-nitrotoluene. A stirred mixture of 124.7 g (0.81 mol) of 2-methyl-3-nitrophenol (Note 1), 113.2 g (0.90 mol) of benzyl chloride, 112.2 g (0.81 mol) of anhydrous potassium carbonate, and 800 mL of dimethylformamide (DMF) is heated at 90°C for 3 hr. Most of the DMF is removed on a rotary evaporator (20 mm) and the oily residue is poured into 400 mL of 1 N sodium hydroxide and extracted with ether (3 × 800 mL). The combined extracts are dried (Na2SO4), filtered, and evaporated to give 203.5 g of yellowish solid. Recrystallization from 1 L of methanol cooled to 0°C affords 177.6 (90%) of 6-benzyloxy-2-nitrotoluene as pale-yellow crystals, mp 61–63°C3 (Note 2). B. (E)-6-Benzyloxy-2-nitro-β-pyrrolidinostyrene. To a solution of 175.4 g (0.72 mol) of 6- benzyloxy-2-nitrotoluene in 400 mL of DMF are added 102.5 g (0.84 mol) of N,N-dimethylformamide dimethyl acetal (Note 3) and 59.8 g (0.84 mol) of pyrrolidine. The solution is heated at reflux (110°C) for 3 hr (Note 4) under nitrogen and allowed to cool to room temperature.
    [Show full text]
  • Catalytic Ethylene Dimerization and Oligomerization Speiser Et Al
    Acc. Chem. Res. 2005, 38, 784-793 reaktion)2 of ethylene, nickel salts could modify the nature Catalytic Ethylene Dimerization of the products from R-olefins to 1-butene. This phenom- and Oligomerization: Recent enon became known in the literature as ªthe nickel effectº1,3 and led to the discovery of the ªZiegler catalysisº4 Developments with Nickel and to the remarkable chemistry developed by Wilke and 5 others over decades. The selective synthesis of C4-C20 Complexes Containing linear R-olefins has become a topic of considerable P,N-Chelating Ligands interest in both academia and industry owing to their growing demand most notably as comonomers with ² ,² FREDY SPEISER, PIERRE BRAUNSTEIN,* AND ethylene [C4-C8 to yield branched linear low-density LUCIEN SAUSSINE³ polyethylene (LLDPE) with impressive rheological and Laboratoire de Chimie de Coordination (UMR 7513 CNRS), mechanical properties6], for the synthesis of poly-R-olefins Universite Louis Pasteur, 4 rue Blaise Pascal, F-67070 and synthetic lubricants (C ), as additives for high-density Strasbourg CeÂdex, France, and Institut Franc¸ais du PeÂtrole, 10 Direction Catalyse et SeÂparation, IFP-Lyon, BP 3, F-69390 polyethylene production and for the production of plas- 7-9 Vernaison, France ticizers (C6-C10) and surfactants (C12-C20). The annual 8 Received February 14, 2005 worldwide consumption of polyolefins is close to 10 tons. Because the demand for linear R-olefins is growing faster - × 6 ABSTRACT in the C4 C10 range (a ca. 2.5 10 tons/year market) than Catalytic ethylene oligomerization represents a topic of consider- in the C12+ range, the selective formation from ethylene able current academic and industrial interest, in particular for the of specific shorter chain R-olefins, which could circumvent R - production of linear -olefins in the C4 C10 range, whose demand the typical, broad Schulz-Flory distributions observed in is growing fast.
    [Show full text]
  • When Phosphosugars Meet Gold: Synthesis and Catalytic Activities of Phostones and Polyhydroxylated Phosphonite Au(I) Complexes
    Article When Phosphosugars Meet Gold: Synthesis and Catalytic Activities of Phostones and Polyhydroxylated Phosphonite Au(I) Complexes Gaëlle Malik, Angélique Ferry and Xavier Guinchard * Received: 23 September 2015 ; Accepted: 20 November 2015 ; Published: 27 November 2015 Academic Editor: Bimal Banik Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1 Avenue de la Terrasse, 91198 Gif sur Yvette cedex, France; [email protected] (G.M.); [email protected] (A.F.) * Correspondence: [email protected]; Tel.: +33-1-69-82-30-66 Abstract: The synthesis and characterization of P-chiral phosphonite-, phosphonate- and thiophosphonate-Au(I) complexes are reported. These novel ligands for Au(I) are based on glycomimetic phosphorus scaffolds, obtained from the chiral pool. The catalytic activities of these complexes are shown in the cyclization of allenols and the hydroamination of 2-(2-propynyl)aniline combined with an organocatalyzed reduction to the corresponding 2-phenyl tetrahydroquinoline. All described gold complexes present excellent catalytic activities. Keywords: gold catalysis; phosphosugars; catalysis; heterocycles; P-stereogeny 1. Introduction One of the major advances of the 21th century in organic chemistry is undoubtedly the increased importance of gold catalysis. Long believed to be useless for catalysis, gold complexes have emerged as powerful tools for the catalysis of myriads of reactions [1–9]. In particular, the gold tolerance towards air, moisture and numerous chemical functionalities renders the use of these catalysts very convenient. However, the bicoordinate linear geometry of gold(I) complexes makes the control of the asymmetry difficult, the chiral ligand being placed in a distal position to the reactive cationic center.
    [Show full text]
  • Fatty Acid Biosynthesis
    BI/CH 422/622 ANABOLISM OUTLINE: Photosynthesis Carbon Assimilation – Calvin Cycle Carbohydrate Biosynthesis in Animals Gluconeogenesis Glycogen Synthesis Pentose-Phosphate Pathway Regulation of Carbohydrate Metabolism Anaplerotic reactions Biosynthesis of Fatty Acids and Lipids Fatty Acids contrasts Diversification of fatty acids location & transport Eicosanoids Synthesis Prostaglandins and Thromboxane acetyl-CoA carboxylase Triacylglycerides fatty acid synthase ACP priming Membrane lipids 4 steps Glycerophospholipids Control of fatty acid metabolism Sphingolipids Isoprene lipids: Cholesterol ANABOLISM II: Biosynthesis of Fatty Acids & Lipids 1 ANABOLISM II: Biosynthesis of Fatty Acids & Lipids 1. Biosynthesis of fatty acids 2. Regulation of fatty acid degradation and synthesis 3. Assembly of fatty acids into triacylglycerol and phospholipids 4. Metabolism of isoprenes a. Ketone bodies and Isoprene biosynthesis b. Isoprene polymerization i. Cholesterol ii. Steroids & other molecules iii. Regulation iv. Role of cholesterol in human disease ANABOLISM II: Biosynthesis of Fatty Acids & Lipids Lipid Fat Biosynthesis Catabolism Fatty Acid Fatty Acid Degradation Synthesis Ketone body Isoprene Utilization Biosynthesis 2 Catabolism Fatty Acid Biosynthesis Anabolism • Contrast with Sugars – Lipids have have hydro-carbons not carbo-hydrates – more reduced=more energy – Long-term storage vs short-term storage – Lipids are essential for structure in ALL organisms: membrane phospholipids • Catabolism of fatty acids –produces acetyl-CoA –produces reducing
    [Show full text]